The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.Stieglitz, Julius
Science
The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.
Stieglitz, Julius
Chemistry, Analytic -- Qualitative
The concentration of hydrosulphide-ion is, therefore, inversely
proportional to the concentration of hydrogen-ion. It is clear that
the addition of a strong acid, readily yielding concentrations of
hydrogen-ion very much greater than 0.95E−4 (the value of [H^{+}]
in a saturated aqueous solution of hydrogen sulphide) will, as the
result of the greatly increased total hydrogen-ion concentration,
reduce the concentration of hydrosulphide-ion to correspondingly
low values. For instance, the presence of 0.1 molar hydrochloric
acid will increase the concentration of hydrogen-ion close to a
thousandfold and will reduce the concentration of hydrosulphide-ion
to 0.9E−7.
For the secondary ionization (see p. 101) of hydrogen sulphide,
HS^{−} ⇄ H^{+} + S^{2−}, we have
[H^{+}] × [S^{2−}] / [HS^{−}] = K_{2}. (III)
The value of this constant has recently been determined[397] and
found to be 1.2E−15. Recalling the fact that the concentrations
[H^{+}] and [HS^{−}] of hydrogen-ion and hydrosulphide-ion, [p201]
respectively, resulting from the primary ionization, are each[398]
0.95E−4, we have for the concentration of the sulphide-ion, in
aqueous solution saturated with hydrogen sulphide at atmospheric
pressure and 25°, [S^{2−}] = 1.2E−15.
Combining equations (II) and (III), we have, further:[399]
[H^{+}]^2 × [S^{2−}] = ‹k› × K_{2} = ‹k›_{2} = 1.1E−23, (IV)
‹which shows, directly, the relation between the concentration
of the sulphide-ion and that of the hydrogen-ion, the relation
of primary importance in considering the precipitation of
metal sulphides in acid solutions.› The ‹concentration of the
sulphide-ion› is, thus, ‹inversely proportional› to the ‹square›
of the ‹concentration› of ‹the hydrogen-ion›. A thousandfold
increase in the concentration of the latter, which is very nearly
the effect produced by the presence of 0.1 molar hydrochloric acid
([H^{+}] = 0.091), reduces the concentration of sulphide-ion in the
saturated aqueous solution a millionfold: If we call [S^{2−}]_{Ac.}
the concentration of the sulphide-ion in the acid solution,
[S^{2−}]_{Ac.} = (1.1E−23) / (0.091)^2 = 1.3E−21, whereas, in the
absence of acid, as found above, [S^{2−}] = 1.2E−15.
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